Novel Side-Chain Type Sulfonated Poly(phenylquinoxaline) Proton Exchange Membranes for Direct Methanol Fuel Cells

Side-chain type sulfonated poly(phenylquinoxaline) (SPPQ)-based proton exchange membranes (PEMs) with different ionic exchange capacity (IEC) were successfully synthesized by copolymerization from 4,4′-bis (2-diphenyletherethylenedione) diphenyl ether, 4,4′-bis (2-phenylethylenedione) diphenyl ether and 3,3′,4,4′-tetraaminobiphenyl, and post-sulfonation process. The sulfonic acid groups were precisely grafted onto the p-position of phenoxy groups in the side chain of PPQ after the convenient condition of the post-sulfonation process, which was confirmed by ¹H NMR spectra and FTIR. The sulfonic acid groups of side-chain type SPPQ degraded at around 325 °C, and their maximum stress was higher than 47 MPa, indicating great thermal and mechanical stability. The water uptake increased with the increasing IEC and temperature. The size change in their plane direction was shown to be lower than 6%, indicating the stability of membrane electrode assembly. The SPPQ PEMs displayed higher proton conductivity than that of main chain. In the single cell test, the maximum power density of side-chain type SPPQ-5 was 63.8 mW cm⁻² at 20 wt% methanol solution and O₂ at 60 °C, which is largely higher than 18.4 mW cm⁻² of NR212 under the same conditions. The SPPQ PEMs showed high performance (62.8 mW cm⁻²) even when the methanol concentration was as high as 30 wt%.